Preparation of vitamin e or tocopherols



derived therefrom are treated with Patented May 1, 1945 NT OFFICE PREPARATION OF VITAMIN E OR I TOCOPHEROLS John D. Cawley,

Rochester, N. Y., assignor to Distillation Products, Inc., Rochester, N. Y., a

corporation of Delaw No Drawing.

2 Claims.

Tocopherols are known to exist in three differ.- ent forms, namely, alpha, beta, and gamma, all of which have vitamin E activity. My invention relates to the preparation of purified substances having vitamin E activity and containing one or more of these tocopherols.

When a vegetable or animal oil or a. product such as crude fatty acids obtained by the acidulation of refinery foots or soap stock is subjected to treatment with inert gas or steam, at scum or sludge-like product can be condensed from the inert gas or steam. This product is obtained in large' amounts during the deodorization of vegetable or animal oils with steam. A common method of separating this material is to place a trap or partial condenser in the line between the vegetable or animal oil treating tank and the condenser or rectifier for the inert gas Or steam. Also it maybe obtained by condensing the steam and separating the material from the condensate by filtering or settling. The material may be removed as a scum from the surface of the condensed steam or byother methods. When vegetable or animal oils steam under vacuum, skimming the condensed water in the barometric leg or basi will yield this material. This scum or sludge has heretofore been a waste product and has been known 'by various names, such as deodorizer sludge, catch-all sludge, catch-all scum, deodorize'r clabber stock, catch basin scum, etc. It is an exceedingly complex mixture, but contains a high percentage (usually 50-60%) of free fatty acids.

I have discovered that .a to'copherol or vitamin E product can be obtained by subjecting the above described sludges, scums, or fract ons thereof to a hydrogenation treatment. ihe hydrogenated product is then dis solved in a solvent and cooled to precipitate the associated substances insoluble in the solvent at low temperature. The solid matter is removed from the solvent and the solvent is then treated to remove the vitamin E therefrom. Although the starting material'has a high content of free fatty acids, I have found that this procedure yields-a product wt 1" his relatively free of these undesirable; substan s well as the other 1m purities present'in'the ginai starting material. To obtain complete, removal of free fatty acids,

concentrated are Application February 25, 1941, Serial No. 380,517

artfor hydrogenating organic substances. one satisfactory method is to mix the scum with a small amount of Raney nickel catalyst. The resulting mixture is agitated with gaseous hydrogen under a pressure of about 25 to 2000 pounds although smaller or greater pressures are tory. A temperatureof between about 20 and 250 is generally used. Temperatures of about 50-200 C. are most satisfactory. Other well known hydrogenation catalysts such as silver. platinum, Palladium, nickel chromite, etc, may

be used. The hydrogenation treatment is prefsolvent in which it is soluble at one temperature but in which it is insoluble or partially. insoluble at a lower temperature. Examples of suitable solvents are the alcohols melting at below about '20 C. such as methyl, ethyl, isopropyl, butyl, etc., and hydrocarbons such as petroleum ether, gasoline, kerosene, 'etc.

satisfactory solvent for most purposes. This mixture can then be filtered to remove catalyst but this step is not necessary. A solution of about 10 to 40% scum in the solvent is a useful range. The higher ,portion of this range is generally to be preferred. Lower or higher concentrations can beused.

The solvent-hydrogenated scum mixture is then cooled to separatethe fatty acids and other impurities present in the scum. A temperature of approximately-15 C. or less, should be used since this results in a satisfactory removal of free fatty acids. Somewhat lower temperatures are preferred, such as 20 C. or less, since they result in substantially complete removal of them:-

" ably is, washed" the mixture of solvent andv hydrogenated scum should preferably be cooled to approximately 20 or less. V

Hydrogenation of these scums can be accomplished by using methods well known. in the prior precipitated solid matter.

purities. The solvent is then separated from the This can be accomplished in a simple manner by filtration or .decantation. A The precipitate may be and preferwith additional solvent at low temperature and solvent extract. i 1 The solvent. portion is then treated to obtain its vitamin E or 'tocopherolcontent. The most satisfactory method is to merely'distill' the,.-solvent off at ordinary or reduced pressure. If a Y low boiling point solvent is used reduced pressure satisfac- Acetone is the most the washings combined with the f Y Buchner funnel at the same increase in tocopherol iected.

of 19.4 and contained 14.6% tocopherol. fraction was mixed with Raney nickel catalyst is unnecessary. If the solvent boils at above approximately 100 C. it would be best to distill it off under reduced pressure. The residue from- Example 1 Crude sludge, containing approximately 50% free fatty acid and 3.4% tocopherol. was hydrogenated at 100-110" and 50 lbs. initial pressure, using 5% Raney nickel, until the hydrogen uptake ceased (3 hours) Without further treatment, 137.5 g. were dissolved in 680 cc. of acetone (20% solution) and let stand at -35 C. overnight. The solids were then filtered off on a temperature and the precipitate washed with about 2 liters of acetone at 35 C. Filtrate and washing were combined and the acetone removed by distillation leaving 42.42 g. of brown oil containing 10.3% tocopherol. Tocopherol yield, 96%. A three fold concentration was ef- Example II Raw semisolid scum was removed from the hotwell of the barometric condenser of a vacuum steam deodorizer in which hydrogenated cottonseed oil was being deodorized. The scum was melted and intimately mixed with 5% by weight of HCl (36% strength), 1% zinc dust and stannous chloride and the mixture heated and 1 centrate which comprises subjecting removed at about 170 C. and 0.1-mm. and discarded. A second fraction of 29% was removed at about 200 C. and .001-mm. It had an acid value This and heated at 100 with hydrogen under a pressure-of pounds. After four hours the mixture was removed and dissolved in acetone to make a 40% solution. This mixture was filtered to remove catalyst and then cooled to about 20 C.

of the group with a cooling bath containing a mixture of dry ice and acetone. The cold mixture was filtered after 2 hours of cooling and the solid precipitate was washed with fresh cold acetone which was then added to the filtrate. The acetone was then removed from the filtrate by distillation leaving a liquid residue of excellent purity and containing approximately vitamin E.

The scum, as received from the refining or deodorizing plants frequently contains foreign bodies which may be removed by straining or filtering. Also it is usually in the form of an emulsion with water. The water can be removed before hydrogenation by heating, straining, cen' trifuging, etc., but this is not essential. The scum usually contains soaps formed from the fatty acids and the substances causing hardness in the water. It is advantageous, but not necessary to acidify to get rid of these soaps and break the emulsion usually present in the scum. It is to be understood that theterm "s'cum as used herein and in the appended claims includes the crude untreated materials as well as partial purification products, including distillates or fractions thereof.

What I claim is:

1. The process for preparing a vitamin E concentrate which comprises subjecting a crude scum which contains tocopherol and which is derived from the steam deodorization of a member of the group consisting of vegetable and animal fats to hydrogenation,'dissolving the hydrogenated scum in a vitamin E solvent in which the hydrogenated scum is substantially soluble at a certain temperature but in which it is at least partially insoluble at a lower temperature, cooling this mixture to a temperature below approximately 15 to cause precipitation of at least the free fatty acid part 0! the scum, separating the liquid or solvent portion and subjecting it to a treatment to remove vitamin E there from.

2. The processior preparing a-vitamin .E cona crude scum which contains tocopherol and which is derived from the steam deodorization of a member consisting of fats to hydrogenation, ed scum in acetone to form tween 10 and 40 per cent scum, cooling ture to a temperature below approximately -20 a solution of be- C. to cause precipitation of at least the free fatty vegetable and animalv dissolving the 'hydrogenatthis mix- CERTIFI GATE OF C ORRECTION Patent No. 2, 7 ,07 May 1, 191

JOHN .D. CAWIEY.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 2, first column, line t9, Exemple I I, for "OJ-mm." read --.Ol-mm.--; and that the said Letters Petent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 5 yof July, A. D. 1915.

Leslie Frazer (Seal) I Acting Commissioner of Patents. 

